A preparation method of the light absorption layer of a copper-indium-gallium-sulfur-selenium film solar cell is provided. The method employs a non-vacuum liquid-phase chemical technique, which comprises following steps: forming source solution containing copper, indium, gallium, sulfur and selenium; using the solution to form a precursor film on a substrate by a non-vacuum liquid-phase process; drying and annealing the precursor film. Thus, a compound film of copper-indium-gallium-sulfur-selenium is gained.
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1. A method for preparing a light absorption layer of copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell, through a non-vacuum liquid phase process, the method comprising the steps of: (1) forming stable clear source solutions of Cu, In, Ga, S, and Se, including (a) forming stable clear source solutions of Cu by dissolving halides of Cu into a solvent selected from the group consisting of at least one of liquid ammonia, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, dimethylsulfoxide, tetrahydrothiophene-1,1-dioxide, pyrrolidone, and a mixture thereof, and adding a solution conditioner therein, wherein said solution conditioner is selected from the group consisting of at least one of chalcogenide of alkali metal and chalcogenide of alkali earth metal; (b) forming stable clear source solutions of In and Ga by dissolving halides of In and Ga into a solvent selected from the group consisting of at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, 2-methyl-1-butanol, isopentanol, sec-pentanol, tert-pentanol, 3-methyl-2-butanol, and a mixture thereof; and (c) forming stable clear source solutions of S and Se by dissolving ingredients of sulfur and selenium into a solvent selected from the group consisting of at least one of ethanolamine, diethanolamine, triethanolamine, isopropanolamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and a mixture thereof, wherein said ingredients of sulfur and selenium are selected from the group consisting of at least one of elemental S and Se, amine salts or hydrazine salts of S and Se; (2) producing a mixed clear solution of Cu, In, Ga, S, and Se by mixing said stable clear source solutions obtained from (1) according to the stoichiometry ratios of Cu, In, and Ga in formula Cu 1-x In 1-y Ga y Se 2-z S z of the light absorption layer of said CIGSS thin film solar cell, and excess sulfur and/or selenium, wherein 0≦x≦0.3, 0≦y≦1, 0≦z≦2, and the excess degree of S or Se is 0%-800%; (3) using said mixed clear solution of (2) to form a precursor thin film on a substrate through a non-vacuum liquid phase process; and (4) drying and annealing said precursor thin film of (3) to produce a CIGSS compound thin film.
A method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell using a non-vacuum liquid phase process. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
2. The method of claim 1 , wherein said halide of Cu of (1) is represented by the formula MX, wherein M is Cu, and X is one or more halogens selected from Cl, Br and I; or said halide of Cu of (1) is represented by the formula MX 2 , wherein M is Cu, and X is one or more halogens selected from Cl, Br and I; or said halide of In, Ga of (1) is represented by the formula M′X 3 , wherein M′ is In and/or Ga, and X is one or more halogens selected from Cl, Br and I; or said halide of Cu, In, Ga of (1) is represented by the formula MM′X 4 , wherein M is Cu, M′ is In and/or Ga, and X is one or more halogens selected from Cl, Br and I.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell as described where the copper halide is CuX or CuX2 (X is chlorine, bromine, or iodine), the indium/gallium halide is M'X3 (M' is indium or gallium, X is chlorine, bromine, or iodine), or the copper/indium/gallium halide is MM'X4 (M is copper, M' is indium or gallium, X is chlorine, bromine, or iodine). The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
3. The method of claim 1 , wherein a) said amine salts of S and Se of (1) are the salts formed by H 2 S and H 2 Se with N—R 1 R 2 R 3 , wherein R 1 , R 2 and R 3 is independently selected from aryl, hydrogen, methyl, ethyl or C 3 -C 6 alkyl; or b) said hydrazine salts of S and Se of step (1) are the salts formed by H 2 S and H 2 Se with R 4 R 5 N—NR 6 R 7 , wherein R 4 , R 5 , R 6 and R 7 is independently selected from aryl, hydrogen, methyl, ethyl or C 3 -C 6 alkyl.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell as described where the amine salts of sulfur and selenium are formed by H2S/H2Se with N-R1R2R3 (R1, R2, R3 are independently aryl, hydrogen, methyl, ethyl, or C3-C6 alkyl), OR the hydrazine salts of sulfur and selenium are formed by H2S/H2Se with R4R5N-NR6R7 (R4, R5, R6, R7 are independently aryl, hydrogen, methyl, ethyl, or C3-C6 alkyl). The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
4. The method of claim 1 , wherein said chalcogenide of alkali metal is A 2 Q, wherein A is selected from the group consisting of Li, Na, K, Rb, Cs and a combination thereof, and Q is selected from the group consisting of S, Se, Te and a combination thereof; and said chalcogenide of alkali earth metal is BQ, wherein B is selected from the group consisting of Mg, Ca, Sr, Ba and a combination thereof, and Q is selected from the group consisting of S, Se, Te and a combination thereof.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell as described where the alkali metal chalcogenide is A2Q (A is lithium, sodium, potassium, rubidium, or cesium; Q is sulfur, selenium, or tellurium) AND the alkali earth metal chalcogenide is BQ (B is magnesium, calcium, strontium, or barium; Q is sulfur, selenium, or tellurium). The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
5. The method of claim 1 , wherein said excess degree of S or Se is 100%-400%.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell as described where the excess sulfur or selenium ranges from 100% to 400%. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
6. The method of claim 1 , wherein, a mole ratio of a total amount of S and Se to a total amount of Cu, In and Ga ranges from 1.75 to 5 in said mixed clear solution of Cu, In, Ga, S and Se of step (2), and a mole ratio of a total amount of S to a total amount of S and Se ranges from 0 to 0.4 in said mixed clear solution of Cu, In, Ga, S and Se of step (2).
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell as described where the mole ratio of total sulfur and selenium to total copper, indium, and gallium ranges from 1.75 to 5, and the mole ratio of total sulfur to total sulfur and selenium ranges from 0 to 0.4 in the mixed solution. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
7. The method of claim 1 , wherein said light absorption layer of CIGSS thin film solar cell of (2) has a formula Cu 1-x In 1-y Ga y Se 2-z S z , wherein 0≦x≦0.3, 0.2≦y≦0.4, 0≦z≦0.2.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell as described where the CIGSS formula is Cu1-xIn1-yGaySe2-zSz, with 0≦x≦0.3, 0.2≦y≦0.4, and 0≦z≦0.2. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
8. The method of claim 1 , wherein said non-vacuum liquid phase process, which is used in step (3) for preparing said precursor thin film, is selected from the group consisting of spin-coating, tape-casting, spray-deposition, dip-coating, screen-printing, ink-jet printing, drop-casting, roller-coating, slot die coating, Meiyerbar coating, capillary coating, Comma-coating or gravure-coating; or said substrate of (3) is selected from any of the group consisting of polyimide, Si wafer, amorphous hydrogenated silicon wafer, silicon carbide, silica, quartz, sapphire, glass, metal, diamond-like carbon, hydrogenated diamond-like carbon, gallium nitride, gallium arsenide, germanium, Si—Ge alloys, ITO, boron carbide, silicon nitride, alumina, ceria, tin oxide, zinc titanate and plastic.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell as described where the non-vacuum liquid phase process for preparing the precursor thin film is spin-coating, tape-casting, spray-deposition, dip-coating, screen-printing, ink-jet printing, drop-casting, roller-coating, slot die coating, Meiyerbar coating, capillary coating, Comma-coating or gravure-coating, OR the substrate is polyimide, Si wafer, amorphous hydrogenated silicon wafer, silicon carbide, silica, quartz, sapphire, glass, metal, diamond-like carbon, hydrogenated diamond-like carbon, gallium nitride, gallium arsenide, germanium, Si—Ge alloys, ITO, boron carbide, silicon nitride, alumina, ceria, tin oxide, zinc titanate or plastic. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
9. The method of claim 8 , wherein said precursor thin film is annealed at a temperature of 250-650° C.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell as described where the non-vacuum liquid phase process for preparing the precursor thin film is spin-coating, tape-casting, spray-deposition, dip-coating, screen-printing, ink-jet printing, drop-casting, roller-coating, slot die coating, Meiyerbar coating, capillary coating, Comma-coating or gravure-coating, OR the substrate is polyimide, Si wafer, amorphous hydrogenated silicon wafer, silicon carbide, silica, quartz, sapphire, glass, metal, diamond-like carbon, hydrogenated diamond-like carbon, gallium nitride, gallium arsenide, germanium, Si—Ge alloys, ITO, boron carbide, silicon nitride, alumina, ceria, tin oxide, zinc titanate or plastic AND where the precursor thin film is annealed at a temperature of 250-650°C. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
10. The method of claim 1 , wherein said precursor thin film is annealed at a temperature of 50-850° C.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell using a non-vacuum liquid phase process where the precursor thin film is annealed at a temperature of 50-850°C. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
11. The method of claim 10 , wherein said precursor thin film is annealed in Se atmosphere at a temperature of 450-600° C. for 10 to 60 minutes, and in S atmosphere at a temperature of 350-550° C. for 10 to 60 minutes.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell using a non-vacuum liquid phase process where the precursor thin film is annealed at a temperature of 50-850°C AND the precursor thin film is annealed in a selenium atmosphere at 450-600°C for 10-60 minutes, followed by annealing in a sulfur atmosphere at 350-550°C for 10-60 minutes. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
12. The method of claim 1 , wherein a thickness of said CIGSS compound thin film of step (4) is 5-5000 nm.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell using a non-vacuum liquid phase process where the CIGSS compound thin film is 5-5000 nm thick. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
13. The method of claim 1 , wherein said adding said solution conditioner thereby stabilizes said clear stable source solutions.
The method for creating the light-absorbing layer of a copper-indium-gallium-sulfur-selenium (CIGSS) thin film solar cell using a non-vacuum liquid phase process where adding the solution conditioner stabilizes the clear source solutions. The method involves: (1) Creating separate, stable, clear solutions of copper, indium, gallium, sulfur, and selenium. (a) Copper solutions are made by dissolving copper halides in solvents like liquid ammonia, ethanolamine, or formamide, with added solution conditioners such as alkali metal or alkali earth metal chalcogenides to stabilize the clear stable source solutions. (b) Indium and gallium solutions are made by dissolving their halides in alcohols like methanol, ethanol, or isopropanol. (c) Sulfur and selenium solutions are made by dissolving elemental sulfur/selenium, amine salts, or hydrazine salts of sulfur/selenium in solvents like ethanolamine or formamide. (2) Mixing these solutions in specific ratios according to the CIGSS formula (Cu1-xIn1-yGaySe2-zSz), with excess sulfur and/or selenium (0-800%). (3) Applying the mixed solution to a substrate to form a precursor thin film using a non-vacuum liquid phase method. (4) Drying and annealing the precursor film to create the CIGSS compound thin film.
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June 29, 2010
August 15, 2017
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